Organo tin derivatives of tetrafluoro-cyclo-butyl acrylic acids

ABSTRACT

WHEREIN R1, R2, R3 AND R4 ARE INDENTICAL OR DIFFERENT AND REPRESENT ALKYL RADICALS HAVING 1 TO 8 CARBON ATOMS, PHENYL RADICALS OR PHENYL RADICALS SUBSTITUTED BY LOWER ALKYL RADICALS AND R5 REPRESENTS HYDROGEN OR THE METHYL GROUP AND THE USE OF THESE COMPOUNDS FOR THE ANTIMICROBIAL FINISHING OF TEXTILES.   CYCLOBUTANE   1,1,2,2-TETRA(F-),3-(R1-SN(-R2)(-R3)-OOC-C(-R5)=CH-),4-R4-   TIN-ORGANIC COMPOUNDS OF THE FORMULA 1

FIPtSF-Ul United States Patent 3,806,530 ORGANO TIN DERIVATIVES 0FTETRAFLUOR0- CYCLO-BUTYL ACRYLIC ACIDS Christoph Dorfelt, Burghausen,Salzach, Klaus Fischer, Kelkheim, Taunus, and Walter Dittmar, Hofheim,Taunus, Germany, assignors to Farbwerke Hoechst Aktiengesellschaftvormals Meister Lucius & Bruning, Frankfurt am Main, Germany No Drawing.Filed July 7, 1972, Ser. No. 269,867 Claims priority, applicationGermany, July 9, 1971,

P 21 34 358.8 Int. Cl. C07j 7/22 US. Cl. 260-429.7 4 Claims ABSTRACT OFTHE DISCLOSURE Tin-organic compounds of the Formula I R1 RSn-O-CC=OHOHCHRr Ra l I ls CFr-CFT- (1') wherein R R R and R areidentical or different and represent alkyl radicals having 1 to 8 carbonatoms, phenyl radicals or phenyl radicals substituted by lower alkylradicals and R represents hydrogen or the methyl group and the use ofthese compounds for the antimicrobial finishing of textiles.

The present invention relates to the antimicrobial finishing oftextiles.

It is already known how to provide textiles with an antimicrobialfinishing, by treating them with the tinorganic compounds such astributyl tin oxide or triphenyl tin oxide (cf. Textilver-edlung 5(1970), 1 p. 9). These compounds have the disadvantage that they cannotbe fixed on textiles, especially textiles made of synthetic fibrematerials, with a resistance to washing and to chemical cleansing.Furthermore, these compounds do not possess any bacteriostatic activityAnother disad vantage is that they adversely affect the dry creasingangles when they are applied together with crease-resistant finishingagents.

It has now been found that the disadvantages described of the knowntin-organic compounds may be eliminated if for an antimicrobialfinishing of textiles tin-organic compounds of the general Formula I areused, wherein R R R and R represent identical or different alkyl or arylradicals and R represents hydrogen or the methyl group.

In the Formula I R R R and R 4 may stand above all for alkyl radicalshaving 1 to 8 carbon atoms, phenyl radicals or phenyl radicalssubstituted by lower alkyl radicals; R R and R preferably representbutyl or phenyl radicals and R is a methyl, ethyl, butyl, propyl orphenyl radical.

The present invention relates to tin-organic compounds of the generalFormula I wherein R R R and R are identical or different and representalkyl radicals having 1 to 8 carbon atoms, phenyl radicals or phenylradicals substituted by lower alkyl radicals and R represents hydrogenor the methyl group.

The invention further relates to a process for preparing thesecompounds, in which 1 mol of a bi-organic tin oxide of the Formula II iscondensed with about 2 mols of a carboxylic acid of the Formula 111R4-OHCH-GH'=G-COOH CFz- Fr Rt (III) the radicals R to R having themeanings mentioned in the Formula I.

The invention also relates to a process for the anti= microbialfinishing of the textiles, in which tin-organic compounds of theabove-mentioned general Formula I are applied onto textiles formsolutions or dispersions, the textiles are dried and then expedientlyheated to high temperatures.

Among the compounds of the Formula I to be used ac-= cording to theinvention for the antimicrobial finishing of textiles, there may bementioned the following com pounds, without any restriction being made:

Tributyltin-B-tetr afluorcyclobutylacrylate,Triphenyltin-fl-tetrafluorocyclobutylacrylate,

Tributyltin- 3-methyl-tetrafiuorocyclobutylacrylate,Triphenyltin-B-methyl-tetrafiuorocyclobutylacrylate,Tributyltin-fl-tetrafluorocyclobutylmethacrylate,Tributyltin-B-methyl-tetrafluorocyclobutylmethacrylate,Triphenyltin-fl-tetrafiuorocyclobutylmethacrylate,Triphenyltin-fi-methyl-tetrafiuorocyclobutylmethacrylate.

The compounds of the Formula I possess a good fungi static andbactoriostatic activity. Attention must also be paid to the resistanceto washing and to chemical cleansing with halogenated hydrocarbons ofthe finishes on textiles obtained with the compounds according to theinvention. The resistance to washing of these finishes may be furtherimproved, if the compounds applied on the textile ma= terial aresubjected to an alkaline after-treatment. When being applied, thecompounds of the Formula I have the surprising advantage that theyprovide on synthetic fibres such as polyamide and polyacrylonitrilefibres, anti microbial effects fast to washing. On the cellulose fibretextiles even 'boilproof finishes may be prepared. In the application ofthe compounds of the Formula I a further advantage is that thesecompounds do not lead to a. yellowing of the textile material. Ascompared with many antimicrobial agents, they do not cause anyadditional soiling, for example on textile floor covering.

Textiles and other materials which may be anti= microbially finishedwith the compounds of the Formula I are for example woven and knittedsuperficial materials, yarns, fleeces, reinforced fleeces, textilelaminated mate rials, feathers as well as synthetic leather. Thetextiles to be antimicrobially finished may consist of natural fibressuch as cellulose fibres, wool, silk or synthetic fibres, as for examplepolyamide, polyacrylonitrile, polyester fibres, polyvinylchloride-elastomeric fibres, inorganic fibres, asbestos and glass fibresand mixtures of such fibres, as

for example made of polyester fibres/cotton, polyester fibres/spunrayon, polyacrylonitrile fibres/spun rayon,

polyester fibres/linen, polyester fibres/wool or polyamide fibres/cotton etc.

The preparation of the compounds of the Formula I by reactingbis-organic tin oxides of the Formula II, for example bis-tributyl tinoxide, with carboxylic acids of the Formula III, for examplefi-tetrafluoro-cyclobutyl acrylic acid or methyl-tetrafluoro-cyclobutylacrylic acid may be carried out according to known processes in asuitable organic solvent such as benzene, toluene and xylene. Thereaction proceeds at elevated temperature, expediently at the boilingtemperature of the solvent under reflux, whereby according to thereaction desired, about 2 mols of the carboxylic acid of the Formula IIIper mol of the bis-organic tin oxide of the Formula II are used. Thewater formed during condensation was eliminated together with thesolvent by azeotropic distillation. The substance left after distillingoff the solvent may be used, if desired, directly, without any furtherpurification, for the antimicrobially finishing according to theinvention.

The tin-organic compounds of the Formula I are soluble in many organicsolvents. Particularly suitable solvents with regard to the textileapplication of these compounds are lower aliphatic alcohols, especiallythose having 1 to 4 carbon atoms. The tin-organic compounds according tothe invention are also soluble in an aqueous, alkaline medium, forexample in aqueous solutions of alkali hy= droxides, alkali carbonatesor -bicarbonates. When being applied onto textiles, they may thereforebe applied from organic solvents, from mixtures of solvent and water andat pH-values above 7 from aqueous solutions or emulsions, for examplethose consisting of chloroor fluorohydrcarbons with water or alcohol.For the antimicrobial finishing of textiles there are generally usedsolutions which show a content of about 10 to 100 g., preferably 15 to40 g., of the tin-organic compounds of the For mula I per liter of bath.This concentration of the finish-= ingbaths mostly insures an effectiveamount of deposit depending on the squeezing out effect. The minimum ofthe effective amount required is about 0.3%, calculated on the goodsweight. There is no upper limit for the amounts of tin-organic compoundsto be applied. HOW- ever, an amount to be applied exceeding about 5%cannot be considered practical for economical reasons. 7

For the antimicrobial finish of textiles, the tin-organic compounds of.the Formula I may be used as such and together with other finishing andbinding agents. It is also possible to apply the tin-organic compoundstogether with. optical brighteners or antistatically effective agents.For finishing textiles whichv consist of cellulose fibres or containcellulose fibres, the tin-organic compounds are expediently applied ontothe textile material with crease resistant finishing agents. In thisprocessespecially in the case of cross-linking under dry conditions-goodboilproof .fungistatic effects can be achieved. The tin-organiccompounds may also be used in the known cross-linking processes oftextiles in the presence of more or less amounts of water. Particularlyadvantageous is the use of tin-organic compounds together with finishingagents which are cross-linking in an alkaline medium. The tinorganiccompounds may also be used in the dyeing of textiles and may be addedfor example to the dyestuff bath or printing paste. By this way,antimicrobial effects are simultaneously obtained with the dyeing orprinting. A special advantage is the application of the tin-organiccompounds together with dyestuffs which can be fixed in an alkalinemedium. It is furthermore possible to apply the tin-organic compoundsonto the textile material together with hydrophobing, oleophobing andflame-proof finishing agents.

The tin-organic compounds of the Formula I may be applied onto the goodto be finished in any manner desired, for example by padding, sloppadding, spraying,

doctoring or according to the exhaustion process. The textiles treatedwith the solutions or dispersions of the tin-organic compounds are driedat room temperature or elevated temperature and expediently heated forabout 1 second to 5 minutes up to high temperatures. The choice of thetemperature depends on the heating time and on the textile material.There are generally used temperatures in the range of about to 220 C. Ithas turned out advantageous to subject the textiles treated with thetin-organic compounds of the Formula I and dried, with solutions ofdiluted alkalis or to apply the compounds of the Formula I to textilespretreated with alkalis and alkaline reaction.

It is also possible to incorporate the tin-organic compounds accordingto the invention into pastes, pigment mixtures and the like for coatingpurposes. The use of the tin-organic compounds together with plasticdisper sions, such as polyacrylate, polyurethane, butadiene-co polymer,polyvinylacetate dispersions or natural latex, is particularlyimportant, if floor covering, for example car pets, needle felts, matsor fleeces shall be finished fun gistatically and bacteriostatically.

In the following examples parts and percentages are by weight unlessstated otherwise.

The antimicrobial eificiency of the textile finishes in the followingexamples was tested according to the meth od described in the periodicalTextilveredlung 5 (1970), pp. 12 to 14. For this purpose, Petri dishesof plastics were fed each with 20 ml. of malt extract-dextrose-agar andthe germs were applied onto the solidified surface as inoculating layer.The ends of the layers were covered with a test cloth (2 x 2 cm.) of thefinished good. After an incubation time of 8 days at 28 C., the growthof the germs on the textile material and in its surroundings (incubation zone) was estimated as follows:

Findings Mark The agar layer over the fabric sample shows the samegrowth intensity of the test germ as the surroundings.= :3. On the agarlayer over the sample only some colonies are grow ing; inhibition ofgrowth in contradistinction. to the surround= in s 2 The agar layer overthe fabric sample does not show any colonies of microorganisms W. un 3No growth on the agar layer above the sample; an inhibition zone notlarger than 2 mm. is clearly visible around the sample... 4

Around the fabric sample there is any inhibition zone of more han2rnmEXAMPLE 1 Fabric samples made of polyamide fibres were impregnated ineach case with the following solutions:

ing machine were compiled in Table L TABLE 1 Growth inhibition (mark)Trichoph. Aspen Solution meat. niacr EXAMPLE 2 The samples of apolyacrylonitrile fabric were treated in each case with the followingsolutions:

Solution A:

Tributyl-tin-fi-(methyl)-tetrafiuoro cyclobutyl acry= late inisopropanol/water (3:1 parts by volume), Solution B:

Triphenyl tin-fi-(methyl)-tetrafluoro-cyclobutyl acrylate inisopropanol/water (3:1 parts by volume) and Solution C (comparison)Tributyl tin oxide in isopropanol/ water (3:1 parts by volume).

The squeezing off effect was 50% by weight The fabric samples were driedat 100 C. and fixed for one minute at 150 C, The finishes prepared withthe solutions A and B have excellent fungistatic effects againstdermatomycetes and soil fungi and yeast.

The following Table 2 resumes the antimicrobial effects after threewashing processes in a washing machine:

TABLE 2 Growth inhibition (mark) Candida Candida Trichoph, albicamalbz'cam Asperqillua Solution meat, St 1 604 niger 533 A t 3 3 3 3 B u 33 3 3 C l 1 1 1 EXAMPLE 3 The samples of a cotton poplin wereimpregnated with solutions of the following composition indicated;

The squeezing off effect was 50% by weighti After pad-dyeing the fabricwas dried and fixed by heat ing for one minute to 180 C, The textilesfinished with the solutions A to C have an excellent fungistatic and a.bacteriostatic effect,

As solvent there is used a mixture of 3 parts by volume of isopropanoland 1 part by volume of water;

After pad-dyeing the samples were dried at C on a stretching frame andthen condensed for 5 minutes at 150 C. The samples of the finishedfabrics show a marked fungistatic effect against dermatoinycetes, soilfungi and blastomycetes and a bacteriostatic effect against Sraphylwcoccus aureuso After two processes in a washing machine, a clear inhibition of growth of Trichophyton mentagrophytes (den matomyces) andAspergillus niger (soil fungus) could be demonstrated in the case of thesamples A to C, On the sample D, however, no efficiency of the finishwas ob== served. Whereas the tin-organic compounds in the solu= tions Ato C have practically no influence on the dry creasing angles of thefabrics, the tributyl tin oxide of the sample D causes a considerablediminution of the dry crease angle EXAMPLE 4 Samples of a cotton fabricwere impregnated in each case with a bath consisting of Solution A:

10 g./l. of tribuytl tin-,B-tetrafiuoro-cyclobutyl acry1- late and,Solution B;

101 g./l., of tributyl tin-/3-tetrafiuorocyclobutyl acry= atew squeezedoff until reaching a weight increase of 70% and dried at 100 C;Isopropanol/water (3:1 parts by volume) is used as solvent, The driedfabric samples were then treated with 5 gt/lu of sodium hydroxidesolution (32% rolled together and packed in a foilr After storing for 18hours in this state, the samples were rinsed, neutralized and dried.

The fabrics have an excellent fungistatic effect against:dermatomycetes, yeasts and soil fungi and a bacteriostatic effect. Itmust be mentioned that these samples show after two processes in washingmachines a strong inhibition of the growth of the fungi on the fabricsample and at the periphery of the sample in the case of Trichophytonmentagrophytes, Candida albicans and Aspergillus nigelg, furthermore inthe case of Staphylococcus aureuso EXAMPLE 5 A polyester fibre fleecewas impregnated on the padding machine with a bath which contained 25parts of a 42% aqueous dispersion of a copolymer consisting of 52% ofbutyl acrylate, 25% of acrylo-= nitrile, 21% of styrene and 2% ofacrylamide,

2 parts of tribuytl tin- 3-(methyl)-tetrafiuorocyclobutyl acrylate and33 parts of isopropanola After squeezing off to reach a weight increaseof 509% the whole was dried and condensed for 7 minutes at C" Thereinforced fleece showed in the test a fungistatic and bacteriostaticeffect against Trichophyton mentagrm phytes, Aspergillus niger andStaphylococcus amen-r0 T7 5% We claim: References Cited 1., Tin-organiccompounds of the Formula I UNITED STATES PATENTS 3,133,942 5/1964 Hahlmmmmmmmmmm m 260-=429.7

5 3,409,652 11/1968 Horrocks m- 260429.7 R: 8 R, Jan-6F, 3,651,1073/1972 Stanback et ai M--. 260429.7

wherein R R R and R are identical or different and a 5 represent alkylradicals having 1 to 8 carbon atoms, phenyl DANIEL WYMAN Pnmary Exammerradicals or phenyl radicals substituted by lower alkyl' A P. DEMERS,Assistant Examiner radicals and R represents hydrogen or the methylgroup 10 2. Tributyl tin-[5-tetrafiuoro-cyclobutyl acrylate. U51, CL

3, Tributyl tin-jS-rnethyl-tetrafluoro-cyclobutyl acrylate 160-15 r,

4c Triphenyl tin-p-methyl-tetrafiuoro-cyclobutyl acry= late,

